JPH0829972A - Photopolymerized photosensitive material - Google Patents

Abstract

PURPOSE:To improve the storage stability of the photopolymerized composition. CONSTITUTION:This photopolymerized photosensitive material is obtained by providing a high molecular polymer layer, which has at least phosphonic acid group or phosphinic acid group in the side chain, on a support and providing a layer of the photo polymerized composition including at least (a) one kind of ethylene unsaturated composition, which is the non-gaseous condition at ordinary temperature, (b) phenyl glycine derivative expressed with the formula, and (c) photo polymerization starting agent. In the formula, R<1> is selected among alkyl group having C1-C12, alkenyl group having C2-C12, alkinyl group having C2-C12, alkoxy group having C1-C8, monocarboxylic acid, ester, amide and phenyl group respectively having C2-C6, alkanol group having C2-C5, and the R<1> can form the condensation polycyclic compound as same as the benzene ring. (n) means 0 or 1. R<2>, R3 are the same group or different group, and they mean hydrogen or a group selected among alkyl group having C1-C12.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive material having a photopolymerizable layer, and more particularly to a highly sensitive photopolymerizable material having excellent storage stability.

[0002]

2. Description of the Related Art Photopolymerizable photosensitive materials are widely used as printing plates, resist materials, hologram sensitive materials and the like.
However, it is known that the storage stability is low. In particular, there was a problem with storage stability at high temperatures or under high temperature and high humidity. As a countermeasure, addition of a polymerization inhibitor or a metal chelating agent is known. Further, addition of a mineral acid or a low molecular weight organic acid to the protective layer, which is disclosed in JP-B-4-21184, JP-A-Sho 6
No. 0-262153, the addition of an acid to the photopolymerizable layer disclosed in JP-A-1-201652 is known.

[0003]

However, the photopolymerizable composition containing the phenylglycine derivative is not sufficient in the above-mentioned method and is excellent in storage stability, especially at high temperature or even when stored for a long time under high temperature and high humidity. A photopolymerizable photosensitive material that does not deteriorate in performance is required.

[0004]

In order to solve the above problems, that is, to improve the storage stability of a photopolymerizable photosensitive material containing a phenylglycine derivative, the present invention has been earnestly studied, and as a result, The invention was completed. That is, the present invention provides a high-molecular polymer layer having at least a phosphonic acid group or a phosphinic acid group as a side chain on a support, and further comprises at least (a) one type of non-gaseous ethylenically unsaturated at room temperature. Compound (b) A photopolymerizable photosensitive material comprising a layer comprising a photopolymerizable composition containing a phenylglycine derivative (c) represented by the general formula 1 and a photoinitiator. Examples of the high molecular weight polymer having a phosphonic acid group and a phosphinic acid group in the side chain used in the present invention include homopolymers and copolymers of vinylphosphonic acid, vinylphosphinic acid, (p-styrylmethyl) phenylphosphinic acid and the like. And copolymers with other vinyl monomers. Of these, polyvinylphosphonic acid is particularly preferable.
The above-mentioned polymer having a phosphonic acid group or a phosphinic acid group in its side chain can be used alone or in combination of two or more. As a treatment method, it is suitable to carry out the dipping treatment in a treatment liquid concentration range of 0.01 to 30% by weight, a liquid temperature range of 10 to 90 ° C., and a treatment time range of 5 to 300 seconds. On the support thus obtained, at least (a) one kind of non-gaseous ethylenically unsaturated compound at room temperature (b) phenylglycine derivative represented by the general formula 1 (c) photoinitiator is contained. There is provided a photopolymerizable composition containing a photopolymerizable photosensitive material provided with a layer composed of the photopolymerizable composition.

The ethylenically unsaturated compound used in the present invention may be any monomer as long as it is a monomer suitable for a chain growth addition reaction initiated by free radicals. Preferable examples include pentaerythritol triacrylate, polyethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and the like. Specific examples of the phenylglycine derivative used in the present invention include N-phenylglycine, N- (3-chlorophenyl) glycine, N-
(2,4 dichlorophenyl) glycine, N- (2-nitrophenylyl) glycine, N- (4-acetylphenyl) glycine, N- (4-nitrophenylyl) glycine, N- (4-cyanophenylyl) ) Glycine, N- (4
-Chlorophenyl) glycine, N- (2-methylphenyl) glycine, N- (2-methoxyphenyl) glycine, N- (2,4-dimethoxyphenyl) glycine, N
-Methyl-N-phenylglycine, N- (3cyanophenyl) glycine, N- (4-carbamoylphenyl) glycine, N- (4-sulfamoylphenyl) glycine, and the like.

The photoinitiator used in the present invention is not particularly limited, but α-carbonyl compound, acyloin ether, aromatic acyloin compound, polynuclear quinone, hexaarylbisimidazole, trihalomethyl-S- Also included are triazine, acridine, phenazine, onium salts such as triphenylsulfonium salts and diaryliodonium salts, titanocene, iron allene complexes and the like.

A sensitizer may be added to the present invention.
Although not particularly limited, preferably cyanine, carbocyanine, merocyanine, aromatic carbonyl, styryl, acridine, thiazine, oxazine, coumarin, polycyclic aromatic hydrocarbon, polyarylamine, pyrylium,
It is at least one dye selected from the group consisting of thiapyrylium and xanthene. Preferably, a thermoplastic high molecular weight organic polymer binder may be present in the composition of the present invention. Types of polymer binders include (1) copolyesters based on terephthalic acid, isophthalic acid, sebacic acid, adipic acid and hexahydroterephthalic acid,
(2) polyamide, (3) vinylidene chloride copolymer, (4) ethylene / vinyl acetate copolymer,
(5) cellulose ether, (6) polyethylene,
(7) Synthetic rubber, (8) Cellulose ester, (9) Polyvinyl ester including polyvinyl acetate / acrylate and polyvinyl acetate / methacrylate copolymer, (10) Polyacrylate and poly α-alkyl acrylate ester such as polymethyl acrylate and poly Ethyl methacrylate, (11) 4,000-4,00
High molecular weight ethylene oxide polymer having a weight average molecular weight of 0,000 (polyethylene glycol), (12) polyvinyl chloride and its copolymers, (13) polyvinyl acetal, (14) polyformaldehyde, (15) polyurethane,
(16) polycarbonate and (17) polystyrene.

In the compositions of the present invention, a particularly preferred polymeric binder is one in which the unexposed photopolymerizable coating is soluble in predominantly aqueous solutions, such as alkaline solutions, but relatively after exposure to actinic radiation. Polymeric binders that are insoluble in it are preferred. Polymers that typically meet these requirements are carboxylated polymers, such as vinyl addition polymers containing free carboxylic acid groups. There are methacrylic acid copolymer, acrylic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer and the like. In addition, there are cellulose having a carboxyl group in the side chain, a polymer having a hydroxyl group in the side chain and a cyclic acid anhydride added thereto, and the like.

In addition, it is desirable to add a small amount of a thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable ethylenically unsaturated compound during the production or storage of the photopolymerizable composition. Suitable thermal polymerization inhibitors include hydroquinone, p-methoxyphenol and di-t.
-Butyl-p-cresol, pyrogallol, di-t-butylcatechol, benzoquinone, 2-mercaptobenzimidazole, N-nitrophenylhydroxyamine primary cerium and the like. The addition amount of the thermal polymerization inhibitor is preferably 0.01 to 5% by weight based on the total composition. Further, if necessary, an inert additive such as a non-polymerizable plasticizer, a dye, a pigment and a filler may be blended to such an extent that the photopolymerizability is not significantly impaired.

The photopolymerizable composition of the present invention can be coated on a wide variety of substrates. By "substrate" herein is meant any natural or synthetic support, preferably one that may be present in the form of a flexible or rigid film or sheet. For example, the material can be a metal sheet or foil, a synthetic organic resin sheet or film, cellulosic paper, fiberboard or the like or a composite of two or more of these materials. Specific materials include alumina plast aluminum, anodized aluminum, aluminum plast polyethylene terephthalate film, polyethylene terephthalate film,
Examples include electrostatic discharge treated polyethylene terephthalate film, polyvinyl alcohol coated paper, cross-linked polyester coated paper, nylon, glass, cellulose acetate film and the like. The particular material will generally be determined by the relevant application purpose. For example, if a printed circuit is manufactured, the material can be a copper coated plate on a fiberboard. In the manufacture of lithographic printing plates, the material can be anodized aluminum.

In the present invention, the thickness of the photopolymerizable composition is
The thickness is 0.1 to 250 μm, preferably 0.5 to 50 μm.
The desired thickness is determined by the application. On the layer of the photopolymerizable composition provided on the substrate, a protective layer made of a polymer having an excellent oxygen barrier property, such as polyvinyl alcohol, is provided in order to prevent a polymerization inhibitory action by oxygen in the air. Alternatively, a cover film such as a polyethylene terephthalate film may be laminated.

The light source used for the exposure is a carbon arc lamp, high pressure, medium pressure, low pressure mercury lamp, xenon lamp, metal halide lamp, argon ion laser, laser such as helium cadmium laser, helium neon laser, fluorescent lamp, Tank stain light and sunlight can be used.

EXAMPLES The present invention will be described in more detail with reference to the following examples, in which parts and% are based on weight. Example 1 A brush-polished aluminum plate having a thickness of 0.24 mm was immersed in 5% sodium hydroxide at 30 ° C. for 1 minute, washed with water, neutralized with nitric acid, and washed with water. Current density 3A in 10% sulfuric acid
/ Dm ² to give a thickness of 3 g / m ² anodizing treatment.
After that, it was immersed in a 0.1% polyvinylphosphonic acid aqueous solution at 35 ° C. for 1 minute, washed with water and dried to obtain an aluminum substrate. Next, apply the photosensitive layer coating liquid of the following composition and dry it in a hot air dryer at 100 ° C
After drying for a minute, a coating film having a thickness of 2.0 g / m ² was obtained.

(Composition of photosensitive layer coating liquid) Poly (methyl methacrylate / methacrylic acid) 52 parts 85/15 molar ratio Molecular weight 80,000 tetraethylene glycol diacrylate 40 parts 2,2 '-(0-chlorophenyl) -4, 4 ', 5,5'-Tetraphenylbisimidazole 5 parts Michler's ketone 3 parts N-phenylglycine 6 parts Methanol 200 parts Ethyl acetate 80 parts Chloroform 120 parts

Next, a protective layer coating solution having the following composition was applied and dried in a hot air dryer at 100 ° C. for 1 minute to provide a protective layer having a thickness of 1 g / m ² to obtain a test piece. (Protective layer coating liquid composition) Polyvinyl alcohol 100 parts (Complete saponification, degree of polymerization 500) Nonionic surfactant 1 part (Neugen EA150 Daiichi Kogyo Seiyaku Co., Ltd.) Water 900 parts The test piece is at 40 ° C and 80% RH After leaving for 10 days,
Imagewise exposed with an ultra-high pressure mercury lamp (Oak's bright room printer), and a negative PS plate developer (Fuji Photo Film, DN-3C).
) It was immersed in a 1: 1 diluted solution (30 ° C.) for 20 seconds, washed with water to remove the uncured portion, and air-dried to obtain a lithographic printing plate. The lithographic printing plate obtained in this way was applied to the Ryobi printing machine 3200MCD.
When 10,000 copies were printed on a high-quality paper using a commercially available black ink, it was possible to print without scumming.

Examples 2 to 4 In Example 1, instead of polyvinylphosphonic acid, the first
Using a polymer having a phosphonic acid group and / or a phosphinic acid group in the side chain shown in the table, the same operation as in Example 1 was repeated and the background stain of the printing plate was evaluated. The printing plate was evaluated in the following three stages. ○: Good △: Partial background stain occurred ×: Background stain occurred

COMPARATIVE EXAMPLE 1 The same operation as in Example 1 was repeated to evaluate the background stain of printing by using 70 ° C. 2% No. 3 water glass in place of the 35 ° C. 0.1% polyvinyl aqueous solution in Example 1. Examples 1 to 4
The results of Comparative Example 1 are shown in Table 1.

[0017]

[Table 1]

Examples 5 to 9 A coating solution for the photosensitive layer having the following composition was applied onto the aluminum substrate described in Example 1 and dried with hot air to obtain a coating film having a thickness of 1.8 g / m ² . (Photosensitive layer coating liquid composition) Poly (methyl methacrylate / methacrylic acid / n-hexyl methacrylate) 52 parts Molar ratio 65/15/20 tetraethylene glycol dimethacrylate 40 parts (η ⁵ -cyclopetadienyl) ( η ⁶ -Toluene) Iron (2) Hexafluorophosphate 5 parts 7-Diethylamino-3 (2-benzimidazolyl) -coumarin 3 parts Phenylglycine derivative 6 parts Methyl ethyl ketone 150 parts Dimethylformamide 150 parts

Next, the same coating solution for protective layer as in Example 1 was applied and dried in a hot air dryer at 100 ° C. for 1 minute, and a protective layer having a thickness of 1.2 g / m ² was provided to obtain a test piece. . The obtained test piece
After standing for 10 days under the conditions of 40 ° C. and 80% RH, imagewise scanning exposure was performed with an argon ion laser (50 mW, beam diameter 25 μ). Then, the developer used in Example 1 was used at 30 ° C. for 23 hours.
It was dipped in seconds, washed with water to remove the uncured portion, and air-dried to obtain a lithographic printing plate. When a printing test was conducted in the same manner as in Example 1, there was no background stain and good printing could be performed.

Comparative Examples 2 to 4 Water glass No. 3 at 70 ° C. and 2% was used in place of the polyvinylphosphonic acid in Examples 5, 7 and 8, and the same operation was repeated to evaluate the background stain of printing. Table 2 shows the results.

[0021]

[Table 2]

[0022]

The photopolymerizable light-sensitive material of the present invention has excellent storage stability and does not deteriorate in developability even after long-term storage. In the case of a lithographic printing plate, stains do not occur on non-image areas. Good printed matter can be obtained.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical indication H05K 3/00 F

Claims (1)

[Claims] 1. A support having at least a phosphonic acid group or
And a polymer layer having a phosphinic acid group in the side chain
And at least (a) at least one non-gaseous state at room temperature
An ethylenically unsaturated compound (b) represented by the following general formula 1
Phenylglycine derivative (c) containing a photoinitiator
Photopolymerizable photosensitive material provided with a layer comprising a photopolymerizable composition
Fee. [Chemical 1]R in the formula¹Is C₁~ C₁₂Alkyl group of C₂~ C₁₂Arche
Nyl group, C₂~ C₁₂An alkynyl group of C₁~ C₈Arco
Xy group, cyano group, alkylthio group, phenoxy group,
C₂~ C₆Monocarboxylic acids and esters of
De, phenyl group, C ₂~ C_FiveAlkanoyl group, ammoni
Umium salt, pyridinium group, nitro group, alkylsulfi
 Nyl group, alkylsulfonyl group, sulfamonol group
To form a condensed polycyclic compound with a benzene ring
Good n is 0 or 1 and R², R³Are the same or different
Is hydrogen or C₁~ C₁₂Alkyl group of
Is chosen from.